A silica-containing bayerite alumina is prepared by reacting aluminum sulfate, sodium aluminate and sodium silicate at a pH of about 10.5 to 11.5, preferably in the presence of finely divided magnesium hydroxide "seeds". The silica-containing bayerite is heated to obtain a hydrothermally stable silica "stabilized" eta alumina which may be used in the preparation of catalytic compositions.
|
1. A method of cracking hydrocarbons which comprises reacting a hydrocarbon feedstock under catalytic cracking conditions in the presence of a cracking catalyst which contains about 1 to 50 weight percent of a composition comprising bayerite, 0.5 to 10 weight percent silica wherein the silica is uniformly distributed throughout the bayerite, and up to about 2 weight percent magnesia whereby said silica acts to inhibit the conversion of said bayerite to theta alumina.
4. A method of cracking hydrocarbons which comprises reacting a hydrocarbon feedstock under catalytic cracking conditions in the presence of a cracking catalyst which contains about 1 to 50 weight percent of a composition comprising eta alumina, 0.5 to 10 weight percent silica wherein the silica is uniformly distributed throughout the eta alumina, and up to about 2 weight percent magnesia whereby said silica acts to inhibit the conversion of said eta alumina to theta alumina.
2. The method of
3. The method of
5. The method of
|
|||||||||||||||||||||||||||||||||||||||
This is a division, of application Ser. No. 07/827,119, filed Jan. 28, 1992, now U.S. Pat. No. 5,304,526, which is a continuation-in-part of application Ser. No. 07/780,680, filed Oct. 18, 1981, now U.S. Pat. No. 5,147,836.
The present invention relates to novel alumina compositions and more particularly to improved bayerite/eta alumina compositions that possess a high degree of hydrothermal stability.
Bayerite, which is converted to eta alumina by heating at temperatures of from about 200 to 800°C, have been used in the preparation of various catalytic compositions including hydrocarbon conversion catalyst.
EP 0385246 describes fluid catalytic cracking (FCC) catalysts that contain a bayerite/eta alumina component that improves the performance of FCC in the presence of hydrocarbon feedstocks that contain nickel.
While bayerite/eta alumina exhibits considerable resistance to thermal degradation at elevated temperatures, it has been found that the high temperature hydrothermal (steam) conditions encountered in commercial FCC cracking units tend to deactivate bayerite/eta alumina components over a relatively short period.
It is therefore an object of the present invention to provide a novel bayerite/eta alumina composition which possesses a high degree of hydrothermal stability.
It is a further object to provide improved bayerite/eta alumina which may be used in the preparation of catalytic compositions.
It is yet another object to provide a method by which commercial quantities of highly stable bayerite/eta alumina may be economically produced.
It is still a further object to provide fluid catalytic cracking catalyst compositions which may be used to crack hydrocarbon feedstocks that contain Ni and/or V.
These and still further objects will become readily apparent to one skilled-in-the-art from the following detailed description and drawings wherein
FIG. 1 is a flow diagram that outlines a preferred method for preparing the novel products of our invention; and
FIG. 2 is a graphic representation of X-ray diffraction data which illustrates the hydrothermal stability of the silica modified bayerite/eta alumina our invention.
Broadly, our invention contemplates bayerite/eta aluminas which contain from about 0.5 to 10 weight percent silica (SiO2), and optionally up to about 2 weight percent magnesia (MgO).
More particularly, we have found that a novel silica containing bayerite may be prepared by reacting aqueous solutions of sodium aluminate, aluminum sulfate and sodium silicate at a pH of about 10.5 to 11.5, preferably in the presence of finely divided magnesium hydroxide "seeds" which function as bayerite crystallization nucleation centers to "direct" to formation of bayerite. The novel silica containing bayerite may then be converted to hydrothermally stable silica containing eta alumina by heating to temperatures of from about 200 to 800°C
The novel silica bayerite possesses the following chemical and physical characteristics:
(1) a chemical composition which includes from about 0.5 to 10, and more preferably 2 to 7 weight percent SiO2 wherein the SiO2 component is dispersed throughout the alumina as a coprecipitated component, and less than 2 weight percent Na2 O, and optionally 0.1 to 2.0 weight percent MgO;
(2) a surface area of 300 to 400 m2 /g after calcination at 538°C for 2 hours;
(3) a pore volume of 0.3 to 0.5 cc/g distributed on pores ranging from 20 to 1500 Å;
(4) an X-ray diffraction pattern which indicates the presence of 70 to 95 weight percent bayerite and 5 to 30 weight percent other alumina(s) including pseudoboehmite.
Upon heating to temperatures of 200 to 800°C, the silica-containing bayerite is converted to silica containing eta alumina which has the following properties:
(1) A chemical composition comprising 0.5 to 10 weight percent SiO2, less than 2 weight percent Na2 O which is uniformly distributed throughout the alumina structure, and optionally 0.1 to 2.0 weight percent MgO;
(2) A surface area of 300 to 400 m2 /g after heating to 538°C in the absence of added steam;
(3) A pore volume of 0.3 to 0.5 cc/g upon heating to 538°C in the absence of added steam.
A preferred method for preparing the compositions of our invention is outlined in the drawing and comprises the following steps:
(1) Preparing aqueous solutions of sodium silicate, aluminum sulfate and sodium aluminate which contain 2 to 25 weight percent silica, 2 to 8 weight percent alumina and 10 to 22 weight percent alumina, respectively;
(2) Preparing a finely divided aqueous suspension of magnesium hydroxide by reacting magnesium sulfate with sodium hydroxide to obtain 0.05 to 0.15 weight percent suspended Mg(OH)2 ;
(3) The reactants are combined in a mixed reaction vessel which contains a water heel heated to a temperature of 30 to 100°C, preferably by first adding the magnesium hydroxide seed suspension (or the reactant precursors thereof): then simultaneously adding the sodium aluminate and aluminum sulfate solutions; and finally adding the sodium silicate solution during the latter part of the reaction period.
(4) The rate of addition of the reactants is regulated to maintain a reaction pH of about 10.5 to 11.5 over the duration of the reaction currently set at 100 minutes.
(5) Upon completion of the reaction/aging step, the precipitated hydrous silica containing bayerite product is recovered by filtration, washed with water to remove soluble sodium sulfate impurities, flash dried to obtain 30-35% total volatiles in powder, and optionally calcined at 200 to 800°C to convert the bayerite to eta alumina.
The silica-containing bayerite/eta alumina of our invention may be advantageously added to FCC catalysts to improve the performance thereof in the presence of nickel. Typically, FCC catalysts which contain a zeolite/molecular sieve component such as synthetic faujasite (type X & Y zeolite), ZSM-5, and/or zeolite beta dispersed in an inorganic oxide matrix such as clay, silica, alumina and silica-alumina hydrogels, may be combined with from about 1 to 50 weight percent of the silica containing bayerite/eta alumina described herein.
In addition, the novel compositions may be used in the preparation of catalyst supports for noble metals, metals, nonmetals and compounds thereof such as oxides, sulfides, halides, chalcogenides, and combinations of said materials.
Having described the basic aspects of our invention, the following examples are set forth to illustrate specific embodiments.
PAC Preparation of Silica Containing BaveriteSodium aluminate, sodium silicate, and aluminum sulfate solutions were prepared as follows:
(a) Sodium aluminate--900 lbs of solution containing 20 weight percent alumina and 17 weight percent Na2 O having a specific gravity of 1.44 g/ml was prepared by reacting Al2 O3 powder to sodium hydroxide solution.
(b) Sodium silicate--42 lbs of 38° Be sodium silicate solution having 3.25 weight ratio SiO2 to Na2 O was diluted with 70 lbs H2 O.
(c) Aluminum sulfate--1200 lbs. of solution containing 7.0 weight percent alumina and 20 weight percent sulfate with specific gravity of 1.28 g/ml was prepared by reacting Al2 O3 powder with H2 SO4.
A 500 gallon agitated reactor was charged with a 185 gallon water heel at 140° F. The reaction temperature was kept in the 140-150° F. range. Then 5 lbs. of magnesium sulfate heptahydrate powder was added, followed by 5 lbs of 50% caustic soda. The pH was between 11.3 and 11.6 and the mixture was permitted to react for 5 minutes to form an aqueous suspension Mg(OH)2 seed particulates. The aluminate flow was then started at a rate of 0.75 GPM and the aluminum sulfate flow was started 5 seconds later at a rate of 0.4 GPM until the pH dropped to 11.0 after which the flow rate was adjusted to maintain a pH of 10.70 to 10.75. Silicate flow was started at a rate of 0.25 GPM after the initial pH decreased to 11.0 (between 5 and 7 minutes). The addition of reactants (strike) was continued for 100 minutes, after which the slurry was stabilized to pH 9.7 with aluminum sulfate. The silica containing bayerite slurry was filtered and washed with 150° F. water on a horizontal vacuum belt filter. The filter cake was collected on trays and oven dried at a temperature of 205° F.
The final product had the following chemical, physical and X-ray (crystalline) properties.
| ______________________________________ |
| Chemical Analysis |
| weight percent T.V. |
| 39.5 |
| weight percent Na2 O |
| 1.24 |
| weight percent SO4 |
| 0.13 |
| weight percent SiO2 |
| 3.95 |
| weight percent MgO |
| 0.35 |
| X-ray Analysis: |
| Bayerite 79% crystallinity |
| Pseudoboehmite Remainder |
| ______________________________________ |
A sample of the silica-containing bayerite of Example 1 was heated to a temperature of 538°C for 120 minutes to convert the bayerite of Example 1 to eta alumina having BET surface area of 381 m2 /g and a nitrogen pore volume of 0.42 cc/g.
A.) Bayerite (Alumina A) was prepared as follows:
Sodium aluminate and aluminum sulfate were prepared according to the methods of U.S. Pat. No. 4,154,812 and kept at 125° F. To 185 gallons of water at 140° F. sodium aluminate was added at a rate of 0.75 gallons per minute. Aluminum sulfate was simultaneously added at a rate to keep the pH constant at 10.75 and precipitate alumina. The precipitation reaction was continued for 100 minutes. Afterwards the flow of sodium aluminate was terminated. The pH of the slurry was adjusted to a final value of 9.7 with additional aluminum sulfate. The precipitated alumina was recovered by filtration and washed with tap water at 150° F. and oven dried.
B.) Silica modified bayerite (Alumina B) was prepared as follows:
The same procedure as part A was used with the following exception. A third stream containing sodium silicate, having 10% SiO2 and 3% Na2 O was added during the precipitation at a rate of one liter per minute. A total of 112 lbs of the sodium silicate was used to give 4% SiO2 on the final product.
The properties of Alumina A and Alumina B are shown in Table I. Upon calcination in air for 2 hours at 1000° F., Alumina B exhibited higher BET surface area and nitrogen pore volume than Alumina A. Upon steaming at atmospheric pressure for 4 and 8 hours at 1500° F. and 4 hours at 1600° F., Alumina B exhibited about 60% greater surface area retention than Alumina A. Furthermore, as shown in FIG. 2, whereas Alumina A undergoes significant transformation to theta-alumina upon steaming for 4 hours at 1600° F., Alumina B still exhibits predominantly eta-alumina with only a minor amount of theta-alumina. Thus the silica-stabilized alumina exhibits both greater surface area and phase stability than the unstabilized alumina.
A.) Catalyst A was prepared as follows:
7.3 kg of ultrastable Y zeolite was blended with 2.95 kg of Alumina A and slurried in 29.7 kg of water. The zeolite and alumina slurry was mixed in a high intensity mixer and milled to a fine particle size. 18.6 kg of this slurry was added to 4.9 kg of clay and 26.7 kg of silica sol, prepared according to the teachings of U.S. Pat. No. 3,957,689 and spray dried. The spray dried catalyst was washed with an ammonium sulfate solution to remove the Na2 O and exchanged with a rare earth chloride solution to obtain 2.6 to 2.7 weight percent rare earth oxide on Catalyst.
B.) Catalyst B, having the same composition as Catalyst A, with the only exception that a silica modified bayerite having 4 wt. % SiO2 (Alumina B) was substituted in place of bayerite, was prepared. Properties of Catalysts A and B are shown in Table II.
Both Catalysts A and B of Example 3 were steamed for 4 hours at 1500° F. in a fluidized bed under atmospheric pressure of steam. After steaming, Catalyst B exhibited a higher matrix area than Catalyst A. The two steamed catalysts were evaluated for their ability to crack a Sour Import Heavy Gas Oil in a microactivity test unit (ASTM D-3907-80). The yield comparison is shown in Table III. The catalyst of the present invention (Catalyst B) yielded lower dry gas (C1 +C2 's), lower LPG (C3 +C4), higher gasoline and higher LCO. The higher yield of LCO, or better bottoms cracking, could be attributed to the higher matrix area of Catalyst B. However, the improved gasoline yield was an unexpected result.
Catalysts A and B were treated with 50% steam at 1500° F. and atmospheric pressure for 12 hours, impregnated with nickel and vanadium naphthenates to a level of 2000 ppm Ni and 2700 ppm V, and treated with steam (30V %) again at 1500° F. and atmospheric pressure for 4 hours. The metals treated catalysts have the properties shown on Table II. The metals treated catalysts were evaluated in the Davison Circulating Riser (DCR) pilot plant. The results of the evaluation are shown in Table IV. Catalyst B was higher in activity than catalyst A, as indicated by the lower catalyst to oil required to achieve a constant level of conversion. In addition, catalyst B yielded lower hydrogen and coke and higher gasoline. This illustrates the improved metals tolerance properties of the silica stabilized bayerite/eta alumina.
| TABLE I |
| ______________________________________ |
| Properties of Bayerite (Alumina A) and |
| Silica-Modified Bayerite (Alumina B) |
| Alumina A |
| Alumina B |
| ______________________________________ |
| Average Particle Size/μ |
| 28 12 |
| Bulk Density/g cm-3 |
| 0.9 0.9 |
| TV 33.6 39.0 |
| % SO4 0.17 0.13 |
| % SiO2 -- 3.95 |
| BET @ 1000° F./m2 g-1 |
| 335 381 |
| N2 PV/cm3 g-1 |
| 0.29 0.42 |
| Steaming Study |
| BET 4 hours @ 1500° F./m2 g-1 |
| 99 154 |
| BET 8 hours @ 1500° F./m2 g-1 |
| 91 147 |
| BET 4 hours @ 1600° F./m2 g-1 |
| 79 122 |
| ______________________________________ |
| TABLE II |
| ______________________________________ |
| Properties of Catalysts A and B |
| Catalyst A |
| Catalyst B |
| ______________________________________ |
| Chemical Analysis |
| Na2 O 0.36 0.38 |
| Al2 O3 33.1 33.7 |
| RE2 O3 2.7 2.6 |
| SO4 0.42 0.49 |
| Physical Properties/2 hours @ 1000° F. |
| Davison Index 6 8 |
| Average Bulk Density/cm3 g-1 |
| 0.72 0.70 |
| Zeolite Area/m2 g-1 |
| 187 197 |
| Matrix Area/m2 g-1 |
| 86 85 |
| Relative Zeolite Intensity |
| 96 91 |
| Average Particle Size/μ |
| 67 71 |
| 4 hours @ 1500° F./100% steam |
| Unit Cell Size/Å |
| 24.29 24.29 |
| Relative Zeolite Intensity |
| 60 64 |
| Zeolite Area/m2 g-1 |
| 124 127 |
| Matrix Area/m2 g-1 |
| 38 43 |
| Metals Test |
| Unit cell size/Å |
| 24.28 24.29 |
| Relative Zeolite Intensity |
| 56 62 |
| Zeolite Area 120 128 |
| Matrix Area 35 43 |
| ppm Ni 2049 2061 |
| ppm V 2740 2720 |
| ______________________________________ |
| TABLE III |
| ______________________________________ |
| Yield Comparison of Catalysts A and B |
| Catalyst A |
| Catalyst B |
| ______________________________________ |
| % Conversion 70 70 |
| C/O 4.28 4.15 |
| Yields |
| H2 .055 .058 |
| C1 + C2 's |
| 2.6 2.4 |
| C3 olefins 4.5 4.4 |
| Total C3 's |
| 6.0 5.7 |
| C4 olefins 4.7 4.5 |
| iso C4 4.2 4.1 |
| Total C4 's |
| 10.0 9.7 |
| C5+ Gasoline |
| 47.7 48.5 |
| LCO 19.5 19.9 |
| HCO 10.5 10.5 |
| Coke 3.6 3.6 |
| Mass Balance 99.96 99.96 |
| ______________________________________ |
| TABLE IV |
| ______________________________________ |
| DCR Constant Conversion Comparison |
| Catalyst Catalyst A |
| Catalyst B |
| ______________________________________ |
| Catalyst to Oil 5.2 4.7 |
| Conversion, vol. % |
| 78 78 |
| H2, wt. % 0.54 0.50 |
| C1 + C2 's, wt. % |
| 3.27 3.02 |
| C3 ═, vol. % |
| 7.6 7.5 |
| nC3, vol. % 2.1 2.1 |
| Total C3 's, vol. % |
| 9.8 9.5 |
| C4 ═, vol. % |
| 8.0 8.3 |
| iC4, vol. % 3.9 3.9 |
| nC4, vol. % 0.9 0.9 |
| Total C4 's, vol. % |
| 12.7 13.0 |
| Gasoline, 430° F., vol. % |
| 61.6 62.4 |
| LCO, 430-640° F., vol. % |
| 12.6 12.6 |
| API 19.0 19.0 |
| Bottoms, 640° F.+, vol. % |
| 9.4 9.4 |
| API 2.1 2.1 |
| Coke, wt. % 8.6 8.2 |
| ______________________________________ |
Cheng, Wu-Cheng, Rudesill, John Allen, Laine, Norman Raymond
| Patent | Priority | Assignee | Title |
| 6375914, | Oct 16 1997 | AB Carl Munters | Method for treating silica gel |
| 6942784, | Sep 22 2000 | Engelhard Corporation | Structurally enhanced cracking catalysts |
| 7981836, | May 24 2006 | UOP LLC | Hydrothermally stable alumina |
| Patent | Priority | Assignee | Title |
| 1958710, | |||
| 2935483, | |||
| 2980632, | |||
| 2988520, | |||
| 3025248, | |||
| 3086845, | |||
| 3096154, | |||
| 3403111, | |||
| 3623837, | |||
| 3864461, | |||
| 4019978, | Aug 29 1972 | Laporte Industries Limited | Process for the production of alumina |
| 4154812, | Mar 25 1977 | W R GRACE & CO -CONN | Process for preparing alumina |
| 4247420, | Mar 23 1979 | W R GRACE & CO -CONN | Hydrocarbon conversion catalyst preparation |
| 4313923, | Dec 29 1980 | HARSHAW CHEMICAL COMPANY, A CORP OF NJ | Method of producing pseudoboehmites |
| 4497907, | Jun 16 1982 | Exxon Research & Engineering Co. | Coprecipitated Si-Al-metal-particle catalyst |
| 4568527, | Nov 06 1984 | Kaiser Aluminum & Chemical Corporation | Utilization of partially calcined alumina as precipitation aid in the Bayer process |
| 4755374, | Jul 18 1986 | Alcoa World Alumina LLC; ALMATIS, INC | Aluminum hydroxide production |
| 4766101, | Dec 05 1984 | RHONE-POULENC SPECIALITES CHIMIQUES LES MIROIRS | Alumina-based catalyst carriers having improved durability/mechanical strength/aging resistance |
| 4780446, | Sep 30 1982 | W R GRACE & CO -CONN , A CONN CORP | Alumina-silica cogel |
| 4849190, | May 05 1986 | PETROFLEX, INDUSTRIA E COMERCIO S A , RUA PARANA, S N , CAMPOS ELISEOS, DUQUE DE CAXIAS-RJ, BRAZIL, A CORP OF BRAZIL | Process for the production of hydrated alumina and process for the treatment of acid wastes |
| 5304526, | Oct 18 1991 | W R GRACE & CO -CONN | Silica bayerite/eta alumina |
| 5306417, | Oct 18 1991 | W. R. Grace & Co.-Conn. | Catalytic cracking process utilizing a silica modified bayerite and/or eta alumina-containing catalyst |
| EP385246, | |||
| GB990720, |
| Executed on | Assignor | Assignee | Conveyance | Frame | Reel | Doc |
| Mar 20 1992 | LAINE, NORMAN RAYMOND | W R GRACE & CO CONN | ASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS | 010910 | /0823 | |
| Mar 23 1992 | RUDESILL, JOHN ALLEN | W R GRACE & CO CONN | ASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS | 010910 | /0823 | |
| Mar 25 1992 | CHENG, WU-CHENG | W R GRACE & CO CONN | ASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS | 010910 | /0823 | |
| Feb 23 1994 | W. R. Grace & Co.-Conn. | (assignment on the face of the patent) | / |
| Date | Maintenance Fee Events |
| Jun 10 2004 | ASPN: Payor Number Assigned. |
| Jun 28 2004 | M1551: Payment of Maintenance Fee, 4th Year, Large Entity. |
| Jun 26 2008 | M1552: Payment of Maintenance Fee, 8th Year, Large Entity. |
| Aug 06 2012 | REM: Maintenance Fee Reminder Mailed. |
| Dec 26 2012 | EXP: Patent Expired for Failure to Pay Maintenance Fees. |
| Date | Maintenance Schedule |
| Dec 26 2003 | 4 years fee payment window open |
| Jun 26 2004 | 6 months grace period start (w surcharge) |
| Dec 26 2004 | patent expiry (for year 4) |
| Dec 26 2006 | 2 years to revive unintentionally abandoned end. (for year 4) |
| Dec 26 2007 | 8 years fee payment window open |
| Jun 26 2008 | 6 months grace period start (w surcharge) |
| Dec 26 2008 | patent expiry (for year 8) |
| Dec 26 2010 | 2 years to revive unintentionally abandoned end. (for year 8) |
| Dec 26 2011 | 12 years fee payment window open |
| Jun 26 2012 | 6 months grace period start (w surcharge) |
| Dec 26 2012 | patent expiry (for year 12) |
| Dec 26 2014 | 2 years to revive unintentionally abandoned end. (for year 12) |